Nanostructured Titanium Alloy And Method For Thermomechanically Processing The Same

ABSTRACT

A nanostructured titanium alloy article is provided. The nanostructured alloy includes a developed structure that has been processed from a combination of severe plastic deformation and non-severe plastic deformation type thermomechanical processing steps, with at least 80% of grains in the developed structure having a grain size≦1.0 microns.

FIELD OF THE INVENTION

The invention relates to a nanostructured material and, more particularly, a nanostructured titanium alloy having a developed structure with enhanced material properties.

BACKGROUND

It is known that microstructure plays a key role in the establishment of mechanical properties. Depending on the processing method, a material's structure can be developed to enhance material properties. For instance, it is possible to modify the grain or crystalline structure of the material using mechanical, or thermo-mechanical processing techniques.

United States Patent Application 2011/0179848 discloses a commercially pure titanium product having enhanced properties for biomedical applications. The titanium product has a nanocrystalline structure, which provides enhanced properties in relation to the original mechanical properties, including mechanical strength, resistance to fatigue failure, and biomedical properties. It is disclosed that the known titanium product is first subject to severe plastic deformation (SPD) using an equal channel angular pressing (ECAP) technique at a temperature no more than 450° C. with the total true accumulated strain e≧4, and then subsequently developed using thermomechanical treatment with a strain degree from 40 to 80%. In particular, the thermomechanical treatment includes plastic deformation performed with a gradual decrease of temperature in the range T=450 . . . 350° C. and the strain rate of 10⁻² . . . 10⁻⁴ s⁻¹.

While this known technique achieves a higher level of mechanical properties for commercially pure titanium, there is a need to increase the level of tensile and/or shear strength, as well as fatigue properties in titanium alloys for various engineering applications, including but not limited to biomedical, energy and aerospace applications.

SUMMARY

In view of these shortcomings, an object of the invention, among others, is to increase the level of strength and fatigue resistance of titanium alloys by developing and refining the alloy's nanostructure.

As a result, a nanostructured titanium alloy article is provided. The nanostructured alloy includes a developed structure that has been obtained from a combination of severe plastic deformation type and non-severe plastic deformation type thermomechanical processing steps, with at least 80% of grains in the developed structure having a size≦1.0 microns.

BRIEF DESCRIPTION OF THE DRAWINGS

Exemplary embodiments of the invention will be described with reference to the accompanying drawings, of which:

FIG. 1 is a micrograph of a known commercially pure titanium alloy taken using electron back scatter diffraction;

FIG. 2 is a micrograph of a nanostructured titanium alloy according to the invention taken using electron back scatter diffraction;

FIG. 3 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the known commercially pure titanium alloy;

FIG. 4 is a graphical representation, obtained using electron back scatter diffraction, showing the grain size distribution of the nanostructured titanium alloy according to the invention;

FIG. 5 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the known commercially pure titanium alloy;

FIG. 6 is a graphical representation, obtained using electron back scatter diffraction, showing the misorientation angle distribution of the nanostructured titanium alloy according to the invention;

FIG. 7 is a graphical representation, obtained using electron back scatter diffraction, showing the grain shape aspect ratio distribution in the longitudinal plane of the nanostructured titanium alloy according to the invention;

FIG. 8 is a graphical representation, obtained using electron back scatter diffraction, showing the grain shape aspect ratio distribution in the transverse plane of the nanostructured titanium alloy according to the invention;

FIG. 9 is a micrograph of the nanostructured titanium alloy according to the invention having a plurality of equiaxed grains, obtained using transmission electron microscopy;

FIG. 10 is a micrograph of the nanostructured titanium alloy according to the invention having a plurality of grains with high dislocation density, obtained using transmission electron microscopy; and

FIG. 11 is a micrograph of the nanostructured titanium alloy according to the invention showing a plurality of sub-grains, obtained using transmission electron microscopy.

DETAILED DESCRIPTION OF THE EMBODIMENT(S)

The invention is a nanostructured titanium alloy that can be used in different industries for production of various useful articles, such as orthopedic implants, medical and aerospace fasteners, and aerospace structural components. In an exemplary embodiment of the invention, a composition of commercially pure titanium, having an α-titanium matrix that may contain a small amount of retained β-titanium particles, is processed to develop the structure to achieve a nanostructure with at least 80% of the grains being ≦1 micron. As a result, the nanostructured titanium alloy exhibits various material property changes such as an increase in tensile strength and/or shear strength and/or fatigue endurance limit. In particular, the nanostructured titanium alloy structure is developed using a combination of thermomechanical processing steps according to the invention. This process provides a developed microstructure having a preponderance of ultrafine grain and/or nano crystalline structures.

FIGS. 1 and 2 show the differences between the starting commercially pure titanium alloy microstructure and the resulting structure of the nanostructured titanium alloy according to the invention.

The workpiece can be comprised from various commercially available titanium alloys known in the art, such as commercially pure titanium, Ti-6Al-4V, Ti-6Al-4V ELI, Ti-6Al-7Nb, Ti—Zr, or other known alpha-beta phase titanium alloys.

Accordingly, in other exemplary embodiments of the invention, an alpha-beta phase titanium alloy is processed from a combination of a severe plastic deformation process type and non-severe plastic deformation type thermomechanical processing steps to develop a nanostructure with at least 80% of the grains being ≦1 micron.

In an exemplary embodiment of the invention, a coarse grain commercially pure titanium alloy is used for the workpiece, which has the following composition by weight percent: nitrogen (N) 0.05% maximum, carbon (C) 0.08% maximum, hydrogen (H) 0.015% maximum, iron (Fe) 0.50% maximum, oxygen (O) 0.40% maximum, and titanium (Ti) as the balance. Additionally, the coarse grain commercially pure titanium alloy may also contain trace impurities.

Other alloys titanium alloys may be used, including but not limited to other commercially pure titanium products, Ti-6Al-4V, Ti-6Al-4V ELI, Ti-6Al-7Nb, and Ti—Zr. Standard chemical compositions of these titanium alloys can be found in Tables 1-3, which identify the standard chemical compositions by wt % max. (ASTM F67-06 Standard Specification for Unalloyed Titanium, for Surgical Implant Applications; ASTM F1295-11 Standard Specification for Wrought Titanium-6Aluminum-7Niobium Alloy for Surgical Implant Applications; ASTM F136-12a Standard Specification for Wrought Titanium-6Aluminum-4Vanadium ELI (Extra Low Interstitial) Alloy for Surgical Implant Applications; Titanium Alloy Ti-6Al-4V, Carpenter Technology Corporation Technical Data Sheet; and U.S. Pat. No. 8,168,012).

TABLE 1 Commercially Pure Ti - Chemical Compositions, wt % max Designation N C H Fe O Ti CP Ti (ASTM Grade 1) 0.03 0.08 0.015 0.20 0.18 balance CP Ti (ASTM Grade 2) 0.03 0.08 0.015 0.30 0.25 balance CP Ti (ASTM Grade 3) 0.05 0.08 0.015 0.30 0.35 balance CP Ti (ASTM Grade 4) 0.05 0.08 0.015 0.50 0.40 balance

TABLE 2 Ti—6Al—4V, Ti—6A1—4V ELI, Ti—6Al—7Nb - Chemical Compositions, wt % max Designation N C H Fe O Al Ti V Ti—6Al—4V 0.05 0.1 0.015 0.40 0.020 5.5-6.75 3.5-4.5 balance Ti—6A1—4V ELI 0.05 0.08 0.015 0.25 0.13 5.5-6.5  3.5-4.5 balance Nb Ti—6Al—7Nb 0.05 0.08 0.009 0.25 0.20 5.50-6.50 6.50-7.50 balance

TABLE 3 Ti—Zr - Chemical Compositions, wt % Designation Zr O Other Ti Ti—Zr 9.9-19.9 0.1-0.3 1.0 max balance

The workpiece, for instance a rod or bar, is subjected to severe plastic deformation (“SPD”) and thermomechanical processing. The combined processing steps induce a large amount of shear deformation that significantly refines the initial structure by creating a large number of high angle grain boundaries (misorientation angle≧15°) and high dislocation density.

In particular, in the exemplary embodiment, the workpiece is processed using an equal channel angular pressing-conform (ECAP-C) machine, which consists of a revolving wheel having a circumferential groove and two stationary dies that form a channel that intersect at a defined angle. However, it is also possible in other embodiments to subject the workpiece to severe plastic deformation using other known process types, including equal-channel angular pressing, equal channel angular extrusion, incremental equal channel angular pressing, equal channel angular pressing with parallel channels, equal channel angular pressing with multiple channels, hydrostatic equal channel angular pressing, cyclic extrusion and compression, dual roll equal channel angular extrusion, hydrostatic extrusion plus equal channel angular pressing, equal channel angular pressing plus hydrostatic extrusion, continuous high pressure torsion, torsional equal channel angular pressing, equal channel angular rolling or equal channel angular drawing.

Firstly, using the ECAP-C machine, the workpiece is pressed into the wheel groove and is driven through the channel by frictional forces generated between the workpiece and the wheel. The workpiece is then processed through the ECAP-C machine at temperatures not greater than 500° C., preferably 100-300° C. The workpiece passes through the ECAP-C machine between 1 and 12 times, preferably 4 to 8 times. The die is set at an angle of channel intersection between ψ=75° and ψ=135°, 90° to 120°, and 100° to 110°. To enable comparable structural evolution, a lower channel intersection angle will require fewer passes and/or higher temperature, and a higher channel intersection angle will require more passes and/or lower temperature. The workpiece is rotated around its longitudinal axis by an angle of 90° between each pass through the ECAP-C machine, which provides homogeneity in the developed structure. This method of rotation is known as ECAP route B_(c). However, in other embodiments, the ECAP route may be changed, including but not limited to known routes A, C, B_(A), E, or some combination thereof.

After the workpiece has been processed using severe plastic deformation from the ECAP-C processing steps, the workpiece is then subjected to additional thermomechanical processing using non-SPD type metal forming techniques. In particular, the thermomechanical processing further evolves the structure of the workpiece, more than the ECAP-C alone. In the exemplary embodiment, one or more thermomechanical processing steps may be carried out, including but not limited to drawing, rolling, extrusion, forging, swaging, or some combination thereof. In the exemplary embodiment, the thermomechanical processing is carried out at temperatures T≦500° C., preferably room temperature to 250° C., and provides a cross-sectional area reduction of ≧35%, preferably ≧65%.

The combination of severe plastic deformation and thermomechanical processing substantially refines the initial structure, which consists of an α-titanium matrix that may contain a small amount of retained β-titanium particles, to a predominantly submicron grain size. In the exemplary embodiment of the invention, the ECAP-C process fragments the starting grain structure by introducing large numbers of twins and dislocations that organize to form dislocation cells with walls having a low misorientation angle<15°.

During thermomechanical processing, dislocation density increases, and some of the low angle cell walls evolve into high angle subgrain boundaries, enhancing strength while retaining usable ductility levels for industrial applications.

In the exemplary embodiment, the resulting nanostructured titanium alloy includes an α-titanium matrix that may contain a small amount of retained β-titanium particles.

FIG. 3 is a histogram showing the grain size distribution in the starting commercially pure titanium alloy, while FIG. 4 is a histogram showing the grain size distribution in the nanostructured titanium alloy according to the invention. The average grain size of the nanostructured titanium alloy is reduced from the starting commercially pure titanium alloy. FIG. 5 shows that the starting commercially pure titanium alloy has 90%-95% of the grain boundaries with misorientation angle≧15°, while FIG. 6 shows that the nanostructured titanium alloy retains 20%-40% of the grain boundaries with misorientation angle≧15°. This distribution contributes to the retention of useful ductility levels.

FIGS. 7 and 8 show the grain aspect ratio distribution in the longitudinal and transverse planes of the nanostructured titanium alloy, which demonstrates an increased proportion of lower grain shape aspect ratio grains in the longitudinal plane compared to the transverse plane.

The size of these dislocation cells and subgrains can be measured by a variety of techniques including but not limited to transmission electron microscopy (TEM) and x-ray diffraction (XRD), in particular the extended-convolutional multi whole profile fitting procedure as applicable to XRD. For instance, FIGS. 9-11 are TEM micrographs showing equiaxed grains, high dislocation density, and a high number of sub-grains in the nanostructured titanium alloy, according to the invention. In FIG. 9, the equiaxed grains are highlighted by continuous lines, while in FIG. 10 the high dislocation density regions are highlighted with continuous lines. In FIG. 11, the grains are highlighted with continuous lines and the sub-grains are highlighted with dotted lines.

Table 4 shows typical room temperature mechanical property levels of the starting commercially pure titanium alloy and the nanostructured titanium alloy according to the invention that can be achieved because of structure development.

TABLE 4 Mechanical Properties Cantilever- Rotating Axial Beam Ultimate Tensile Ultimate Fatigue Fatigue Tensile Yield Total Area Shear Endurance Endurance Strength Stress Elongation Reduction Strength Limit* Limit* Material (MPa) (MPa) (%) (%) (MPa) (MPa) (MPa) Starting 784 629 27 50 510 575 450 Titanium Alloy Nanostructured 1200 1050 10 25 650 700 650 Titanium Alloy *Fatigue endurance limit measured at 10⁷ cycles

Table 4 clearly demonstrates that the resulting nanostructured titanium alloy exhibits various material property changes, such as increased tensile strength and/or shear strength and/or fatigue endurance limit. In particular, the nanostructured titanium alloy according to the exemplary embodiment of the invention has a total tensile elongation greater than 10% and a reduction of area greater than 25%. In addition, the nanostructured titanium alloy has at least 80% of the grains having a size≦1.0 micron with approximately 20-40% of all grains having high angle grain boundaries, and ≧80% of all grains have a grain shape aspect ratio in the range 0.3 to 0.7. Additionally, the nanostructured titanium alloy article has grains having an average crystallite size below 100 nanometers and a dislocation density of ≧10¹⁵ m⁻².

Thus, the invention provides a nanocrystalline structure having enhanced properties from the starting workpiece, as a result of severe plastic deformation and thermomechanical processing.

Titanium alloys that may be used in accordance with the present invention include commercially pure titanium, Ti-6Al-4V, Ti-6Al-4V ELI, Ti—Zr, or Ti-6Al-7Nb. The nanostructured titanium alloy in accordance with the present invention can be used to produce useful articles with enhanced material properties, including aerospace fasteners, aerospace structural components, as well as articles for medical applications, such as spinal rods, screws, intramedullary nails, bone plates and other orthopedic implants. For example, the invention may provide aerospace fasteners comprised of nanostructured Ti alloy having increased ultimate tensile strength, such as above 1200 MPa, and increased shear strength, such as above 650 MPa.

The foregoing illustrates some of the possibilities for practicing the invention. Many other embodiments are possible within the scope and spirit of the invention. It is, therefore, intended that the foregoing description be regarded as illustrative rather than limiting, and that the scope of the invention is given by the appended claims together with their full range of equivalents. 

What is claimed is:
 1. A nanostructured titanium alloy article, comprising: a developed α-titanium structure processed from a combination of a severe plastic deformation process type and non-severe plastic deformation type thermomechanical processing steps and having ≧80% of grains in the developed a-titanium structure have a size≦1.0 micron.
 2. The nanostructured titanium alloy article according to claim 1, wherein the developed structure has a dislocation density≧10¹⁵ m⁻².
 3. The nanostructured titanium alloy article according to claim 1, wherein 20-40% of the grains in the α-titanium matrix have high angle grain boundaries with a misorientation angle≧15°.
 4. The nanostructured titanium alloy article according to claim 1, wherein ≧80% of all grains in the α-titanium matrix have a grain shape aspect ratio that is in a range of 0.3 to 0.7.
 5. The nanostructured titanium alloy article according to claim 1, wherein the severe plastic deformation process type is equal-channel angular pressing-conform.
 6. The nanostructured titanium alloy article according to claim 1, wherein an average crystallite size is ≦100 nanometers.
 7. The nanostructured titanium alloy article according to claim 6, wherein a dislocation density is ≧10¹⁵ m⁻².
 8. The nanostructured titanium alloy article according to claim 7, wherein 20-40% of the grains have high angle grain boundaries with a misorientation angle≧15°.
 9. The nanostructured titanium alloy article according to claim 8, wherein ≧80% of all grains have a grain shape aspect ratio in a range from 0.3 to 0.7.
 10. The nanostructured titanium alloy article according to claim 9, wherein the developed structure has an ultimate tensile strength≧1200 MPa.
 11. The nanostructured titanium alloy article according to claim 10, wherein the developed structure has a total tensile elongation≧10%.
 12. The nanostructured titanium alloy article according to claim 11, wherein the developed structure has an area reduction≧25%.
 13. The nanostructured titanium alloy article according to claim 12, wherein the developed structure has an ultimate shear strength≧650 MPa.
 14. The nanostructured titanium alloy article according to claim 13, wherein the developed structure has an axial fatigue endurance limit≧700 MPa measured at 10⁷ cycles.
 15. The nanostructured titanium alloy article according to claim 14, wherein the developed structure has a cantilever-rotating beam fatigue endurance limit≧650 MPa measured at 10⁷ cycles.
 16. The nanostructured titanium alloy article according to claim 1, wherein the developed structure consists of commercially pure titanium.
 17. The nanostructured titanium alloy article according to claim 16, wherein the developed structure is α-titanium matrix having retained β-titanium particles.
 18. The nanostructured titanium alloy article according to claim 1, wherein the developed structure consists of Ti-6Al-4V.
 19. The nanostructured titanium alloy article according to claim 1, wherein the developed structure consists of Ti-6Al-4V ELI.
 20. The nanostructured titanium alloy article according to claim 1, wherein the developed structure consists of Ti—Zr.
 21. The nanostructured titanium alloy article according to claim 1, wherein the developed structure consists of Ti-6Al-7Nb.
 22. The nanostructured titanium alloy article according to claim 1, wherein the developed structure has a composition by weight percent: nitrogen (N) 0.05% maximum; carbon (C) 0.08% maximum; hydrogen (H) 0.015% maximum; iron (Fe) 0.50% maximum; oxygen (O) 0.40% maximum; and a balance of titanium (Ti) and trace impurities.
 23. A method for making a nanostructured titanium alloy, comprising the steps of: providing a workpiece of commercially pure titanium alloy; inducing severe plastic deformation to the workpiece using an equal-channel angular pressing-conform machine at temperatures≦450° C. and having a die set at a channel angle of intersection between ψ=75° and ψ=135°; and subjecting the workpiece to thermomechanical processing at temperatures≦450° C. to prepare an article having a cross-sectional area reduction≧35%. 